NL8501707A - PREPARATION FOR EXTENDING THE EFFECT OF HERBICIDES AND EXTENDED HERBICIDE PREPARATIONS. - Google Patents

Description

* V * NL 32920-Kp / cs

Preparation for extending the action of herbicides and herbicidal preparations with an extended action.

The invention relates to preparations (extenders) for use for extending the action of herbicides with active ingredients thiol carbamate derivatives, as well as herbicidal preparations with a prolonged action with active ingredients thiol carbamate derivatives and optionally an antidote, characterized in that to effect the prolonged action, the compositions contain the diamino-methane derivatives of the general formula 3 of the formula sheet wherein 10 R substituents independently of one another are C 1-8 alkyl groups or C 2-4 alkenyl groups, unsubstituted or substituted by an alkyl group.

The alkyl group preferably contains 1-4 carbon atoms. Preferred alkyl groups are, for example, a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tertiary butyl group.

A preferred alkenyl group is the allyl (2-propenyl) group.

Preferred diaminomethanes of the general formula * 3 of the formula sheet are those containing at least two allyl groups, in particular the Ν, Ν'-diallyl derivatives.

Most preferred are the N 2 dialkyl-N 3 -diall diaminomethanes.

Thiol carbamate derivatives are widely used in agricultural practice as active ingredients of effective herbicides. Thiol carbamates and herbicide preparations containing thiol carbamates therein are described, for example, in U.S. Pat. Nos. 2,913,327 and 3,175,897. Of these compounds, S-ethyl-N, N-dipropylthiol carbamate (EPTC), S-propyl-N, N-dipropylthiol carbamate (vernolate) and S-ethyl - Ν, Ν-diisobutylthiol carbamate (butylate) are commonly used in agriculture .

In addition to the excellent herbicidal action, however, the thiol carbamates have the drawback that they can damage the suitable cultivated plants. To prevent this, they are often combined with antidotes (protective agents -2 * - / 4 '4 - 2 parts). Antidotes suitable for the damage and in particular the maize damage effect of herbicide preparations containing thiol carbamate derivatives are described, for example, in the Belgian patents Nos. 782,120 and 5,806,038, as well as in U.S. Pat. Nos.

3,893,838 and 3,931,313 as well as in Hungarian Pat. Nos. 165,736, 176,784 and 168,977. Of these antidotes, Ν, Ν-diallyldichloroacetamide, as disclosed in Hungarian Pat. 165,736, most commonly used in the land-10 construction practice.

The use of antidotes associates a suitable selectivity with the excellent herbicidal action of the preparations containing thiol carbamate derivatives. In view of the possibility of using antidotes, reference is made to the above-mentioned special literature and in particular the above-mentioned patents.

In addition to the favorable herbicidal action and the appropriate selectivity, the optimal duration of the activity is another important requirement for herbicides.

Herbicide preparations containing thiol carbamate derivatives are usually sprayed over the soil surface prior to sowing. The concentration of the thiol carbamate derivatives is high in the top layer of the soil, which means that the herbicidal action is most intensive just after spraying. However, the concentration of the thiol carbamate derivatives decreases rapidly in the soil due to a number of factors, whereby after a few days the thiol carbamate derivatives are practically no longer detectable.

One reason for this decrease in concentration is the volatility of the active ingredients. This can be prevented by introducing the active ingredients into the soil to a depth of 5 cm after spraying them on the soil.

Another reason for the loss is the rapid decomposition of the thiol carbamate derivatives in the soil due to microbial and physicochemical factors. This decomposition occurs more quickly in fields where thiol carbamate type herbicides have been used previously and repeatedly.

The rapid decomposition of thiol carbamates in the soil §501707 *. 4 - 3 - can be delayed by using the so-called extenders, whereby the herbicidal action and the duration of the action of the thiol carbamates are considerably enhanced, with the result that the weed control becomes more effective and economical than before.

Herbicide formulations, which additionally contain extenders, are disclosed in the published Hungarian patent applications Nos. 783/82 and 3383/82. In accordance with the first-mentioned application, in addition to the thiolcarbamate active ingredients, various substituted 4-phenyl-1,2,3-thiadiazole derivatives are applied to the soil, while according to the latter patent application, tertiary amines, for example di-allylamine, are used. The rate of decomposition of the thiol carbamate derivatives decreases significantly by the use of the above compounds, resulting in a prolonged action.

According to the known methods, the extenders are used in an amount of 2 to 4 ppm calculated on the basis of the soil.

It is an important requirement that the extenders used in practice be easily produced and inexpensive. In addition, these extenders must be able to operate in low doses and effectively prolong the action of the thiol carbamates. However, extenders known to date do not meet these practical requirements.

Examination of extenders, which are easier to prepare and more effective than the known ones, has shown that the above requirements are satisfactorily met by using the diaminomethanes of the general formula 3 of the formula sheet than by the extenders of the state of the art.

The diaminomethane derivatives of the general formula III of the formula sheet are prepared in a manner known per se. Here, 1 mole equivalent of a secondary amine of the general formula r2nh - in which R has the above meanings - is reacted with 0.5 mole equivalent formaldehyde in an aqueous solution.

8501707 4 '5 - 4 -

The product obtained is separated from the water phase, dried and optionally distilled. The crude product obtained after drying is suitable for the present practice.

The preparation of the compounds of the general formula 3 of the formula sheet is illustrated in detail by the following examples.

The known Ν, Ν, Ν ', N'-tetraallyldiaminomethane can be prepared, for example, by using a method as described in the literature / J.Am. Chem. Soc. 483, 10 (1956); Chem. Abstr. 50, 13040 (1956] /, which preparation takes place as follows.

EXAMPLE 1

Preparation of Ν, Ν, Ν ', N'-tetraallyl diaminomethane

Diallylamine (97.2 g, 122.4 ml, 1 mol) was weighed into a 250 ml round bottom flask equipped with a mechanical stirrer, reflux condenser, thermometer and dropping funnel. Aqueous formaldehyde solution (40.5 ml, 37 wt%, 0.5 mol) was added slowly with stirring at such a rate that the temperature remained below 50 ° C. After completion of the addition, the mixture was stirred with heating in a water bath for 2 hours, then the mixture was cooled, separated from the water phase and dried over anhydrous sodium sulfate to give 100.1 g (97 .0%) of a dried crude product yielding, after distillation, 97 g (94.5%) of the pure title compound with a boiling point of 96-98 ° C / 2 kPa, n ^ = 1.4670 (n ^ = 1.4668 according to the literature).

EXAMPLE 2

Preparation of N 2 - diallyl - N 3 - diethyldiaminomethane. Ethylallylamine (85.0 g, 1 mol) was weighed into a 250 ml round bottom flask equipped with a mechanical stirrer, reflux condenser, thermometer and dropping funnel. Aqueous formaldehyde solution (40.5 ml, 37 wt%, 0.5 mol) was added with stirring while the mixture was stirred and at a rate such that the temperature remained below 60 ° C. After the addition, the mixture was stirred in a hot water bath for 2 hours, then the mixture was cooled, separated from the 8501707 * 4-5 aqueous phase and dried over anhydrous sodium sulfate to give 89 g (98%) of a dried crude product which, after distillation, yielded 83.7 g (92%) of the pure title compound as a colorless Fluid, bp 78-80 ° C / 2 kPa, 1.4431.

The diaminomethanes of the general formula III of the formula sheet, prepared in an analogous manner as described in Examples 1 and 2, as well as their physical properties (boiling point and refractive index) are listed in Table A.

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The application described in Hungarian patent application no. 783/82 extenders described contain substituted 4-phenyl-1,2,3-thiadizole derivatives, the preparation of which involves complicated intermediates as starting materials, with the result that these types of extenders are expensive. For example, the final stage of the synthesis of the 4- [2'-N-15 - (311-trifluoromethylphenyl) -carbamoyloxyphenyl] -1,2,3-thiadiazole, according to the above patent application, comprises the reaction of 4- (2'-hydroxyphenyl) -1,2,3-thiadiazole with 3-trifluoromethylisocyanate under anhydrous conditions in the presence of triethylamine in dichloromethane as a solvent.

The diaminomethanes of the invention can be prepared from known simple amines, some of which are commercially available. The process for the preparation of the diaminomethanes according to the invention comprises a one-stage condensation reaction and is particularly simple from a technological point of view and provides high yields. The aqueous formaldehyde solution used in the present process is an inexpensive industrially produced material.

The most effective extenders, which are disclosed in Hungarian Patent Application No. 3383/82 (ie, diallyl and alkylallyamines) are even more volatile than the volatile EPTC, the latter compound having a short duration of action, which means that the former extenders themselves had a short duration. For example, the boiling point of ethylallylamine is 82-84 ° C and that of EPTC 232 ° C at atmospheric pressure.

In contrast, the boiling points of the diaminomethane derivatives of the invention are much higher than those of the suitably substituted known secondary 85 0 1 7 0 7 * * 8 -amines. According to the data listed in Table A, the boiling points of the diaminomethanes of the invention are approximately the same at 2 to 2.7 kPa pressure as those of the suitable secondary amines at atmospheric pressure. In relation to atmospheric pressure, this means that the boiling points of the diaminomethane derivatives according to the invention are about 100 ° C higher than those of the corresponding secondary amines. This means that the danger of evaporation of the extender from the top layer of 5 cm of soil within a short period of time has practically been avoided, whereby the desired effect can be achieved.

The diaminomethanes of the general formula 3 of the formula sheet according to the invention are suitable for prolonging the action of herbicide preparations containing thiolcarbamate derivatives, in particular those preparations, which contain thiol carbamates of the general formula 1 of the formula sheet as active ingredient. in which formula R 1 / R 1 and R 3 independently represent a C 1-4 alkyl group; or R 1 or R 3 is a C 4-8 cycloalkyl group; or R. | and R2 together represent a saturated ring with 5-7 ring atoms.

The herbicidal compositions containing the thiolcarbamate derivatives as active ingredients may also contain an antidote (protective agent) for enhancing selectivity. The suitable antidotes for the thiol carbamates-containing preparations, in particular the thiol carbamates of the general formula 1 of the formula sheet as active ingredient, are preferably the dichloroacetamide derivatives of the general formula 2 of the formula sheet, in which RR R and R5 are independently a C 1-4 alkenyl group, a (C 1-4 alkoxy) - (C 1-4 alkoxy) - (C 1-4 alkyl) group, or a (C 1-4 alkenyl) aminocarbonyl (C 1-4 alkyl) group; or R4 and R4 together form a saturated ring with 4-7 ring atoms, optionally interrupted by an oxygen atom and optionally substituted with at most three methyl or C 4-8 cycloalkyl groups.

2-Methyl-2-dichloromethyldioxolane and 1,8-naphthalene-40 dicarboxylic anhydride can also be used as preferred antidotes. 8501707-9 * *.

The extenders according to the invention are particularly suitable for extending the duration of the action of herbicide preparations containing S-ethyl-N, N-di (n-propyl) thiol carbamate, S- (n-propyl) -N N-di (n-propyl) -thiol carbamate, 5-S-ethyl-N, N-diisobutylthiol carbamate, S-ethyl-N, N-hexamethyl-thiol carbamate or S-propyl-N-ethyl-N-butyl thiol carbamate as active ingredient, possibly together with antidotes. The necessity and success of the use of extenders are not affected by the presence of the antidotes used to enhance the selectivity of the active thiol carbamate containing preparations. The most suitable antidotes are Ν, Ν-diallyldichloroacetamide, N-allyl-N- (ethoxyethoxy-methyl) -dichloroacetamide, 2,2,5-trimethyl-N-dichloroacetyl-oxazolidine, Ν, Ν-hexamethylenedichloroacetamide, 2-cyclohexyl-15 -3-dichloroacetyloxazolidine, N-allyl-N-dichloroacetylglycine allylamide, 2-methyl-2-dichloromethyl dioxolane and 1,8-naphthalene dicarboxylic anhydride.

The extender preparations according to the invention and the thiol carbamate derivatives and antidote-containing preparations 20 can be used together in the form of a mixture or applied separately one after the other and on the ground, especially during the period of emergence of the plants.

After successive application, care should be taken to ensure that the period between application of the extender 25 and the herbicide preparation is as short as possible.

The mass ratio of the extender to the active thiol carbamate of the herbicide preparation can vary within wide limits. This ratio depends on the physical and chemical properties of the extender and the thiol carbamate derivative as well as on the cultivated plant, weeds, the properties of the soil and further on factors known to the skilled worker, or easily understood by the skilled worker. be determined.

In the compositions of the invention, the mass ratio of the herbicidally active ingredient to the extender is generally 25: 1 to 1: 1, usually from 10: 1 to 4: 1, and preferably 6: 1.

The amount of the extender used mainly depends on the thiol carbamate decomposition capacity of 850170?

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- 10 - the ground; this amount can be 0.2-10 kg / ha, usually 0.5-5 kg / ha, preferably 1-2 kg / ha.

The herbicidal compositions of the invention may contain the herbicidally active ingredient and the extender in the above-mentioned ratio. The ratio of the herbicidally active ingredient to the antidote used is no different from the known ratios commonly employed in practice. The total active ingredient content can generally range from 0.1-95 wt%, preferably 1-90 wt%. Naturally, these preparations contain the highly concentrated preparations as well as the preparations ready for use prepared from the concentrates by dilution. The compositions, for example, mixed in a tank or in a spraying device just before use from a herbicide preparation, which optionally contains an antidote and an extender preparation, and which is optionally diluted, also fall within the scope of the invention. The active ingredient content of the formulations containing only the extender separately may range from 0.1-95 wt%, preferably from 1-90 wt%.

The preparation according to the invention can be in the form of solid or liquid preparations, suitable for agricultural practice, while the preparation and application is made possible by the physical and chemical properties of the active ingredient (s). The formulations contained the active ingredient (s) together with a solid or liquid carrier acceptable for agriculture in addition to surfactants.

The formulations may also contain other additives which have a beneficial effect on the desired effect, reduce the volatility of the active ingredients or make application easier. Such additives are, for example, protective colloids, thickeners, adhesives, stabilizers, solid carriers with high adsorption capacity, such as starch, etc. In addition to the amount of the active ingredient (s) as defined above, the compositions of the invention generally contain 1-99% by weight of a solid or liquid carrier and optionally 0.1-25% by weight of a surfactant. dust.

8501707

+ V

- 11 -

Any organic or inorganic, agricultural acceptable material of natural or artificial origin can be used as a carrier, such as, for example, clay, natural or artificial silicates, silicic acid, dolomite, kao-5 line, diatomaceous earth, ground plant products, starch and the like as solid carriers ? water, alcohol, esters, ketones, mineral oil fractions, aromatic, aliphatic or cyclic hydrocarbons, halogenated hydrocarbons, dimethyl formamide, dimethyl sulfoxide, N-methylpyrolidone and the like as liquid carriers.

The surfactant can be an emulsifying, dispersing, or wetting agent of either the ionic and / or nonionic type. Examples of these additives are the salts of lignin sulfonic acid, phenol sulfonic acid and naphthalene sulfonic acid? the polycondensation products of ethylene oxide with fatty acid alcohols, fatty acids or fatty acid amides? alkyl aryl sulfonates, substituted phenols, such as alkyl phenols and aryl phenols, and polyoxyethylated phenols.

With regard to the suitable surfactants, reference is made to the literature, for example the relevant chapters of "Surfactant Science Series",

Ed. Marcel Dekker, Inc., New York. Usually, when the active ingredient or ingredients are insoluble in water and water is used as an auxiliary material, eg for dilution, the presence of at least one surfactant is necessary.

The solid preparations according to the invention can be powders, dust-like materials or granulates. The liquid preparations, ie, the preparations used in a liquid form, may be solutions, emulsifiable concentrates, emulsions, concentrated suspensions, wettable powders, sprayable powders or pastes. The concentrated preparations can be suitably diluted.

The preparations are prepared in a manner known per se.

The compositions of the invention can be used in conjunction with other plant protection agents, such as herbicides, pesticides, fungicides, bactericides and plant growth regulators. In general, any plant protection agent is suitable for the combined use, which is compatible with the thiol carbamate derivatives 85017C 7-12.

The invention also relates to a method for the protection of plants, the main aspect of which is to treat the plants or the soil, which is sown with the 5 seeds, with either a simultaneous or successive herbicide preparation with the active ingredient thiolcarbamate derivative (or - derivatives) and with the extender preparation according to the invention, optionally in the presence of an antidote. This treatment can be carried out using a composition with the active ingredient thiol carbamate and the extender and optionally an antidote. The active ingredients are used in an amount suitable for achieving effective weed control.

The use of the preparations, optionally in a suitably diluted form, can be realized according to the usual methods and devices, for example by spraying, spraying, applying powder, spreading and the like.

The following examples are intended to illustrate the ingredients and formulation of some of the characteristic representatives of the formulations containing the plant protectants of the invention and an antidote without any limitation of the invention.

EXAMPLE I

Preparation of an emulsifiable concentrate S-ethyl-N, N-di (n-propyl) -thiol carbamate (40 parts by weight) was mixed with N, N, N ', N'-tetraallyldiaminomethane extender / 8 parts by weight; compound (aVJ, as well as with oxyethylated anhydrosorbitol monostearate (1 part by weight Tween 60) and xylene (51 parts by weight) were added to give a concentrate with an active ingredient content of 48% by weight, which preparation is a 5: 1 mass ratio of the herbicidally active ingredient to the extender This concentrate can be easily transported and stored and, after dilution with water before use, it can be applied in the form of a stable sprayable emulsion.

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EXAMPLE II

Preparation of an emulsifiable concentrate S-ethyl-N, N-di (n-propyl) -thiol carbamate (20 parts by weight) was dissolved in xylene (47 parts by weight), after which N, N "-5-diethyl-Ν Ν'-diallyldiaminomethane gew 1 part by weight compound (b | 7 and a polyoxyethylene fatty acid ester (2 parts by weight) were added. The total active ingredient content of this preparation was 28.6% by weight, while the mass ratio of the herbicide active ingredient until the extender was 20: 1.

EXAMPLE III

Preparation of a concentrate N, N, N ', Ν-Tetraallyldiaminomethane extender / 95 parts by weight; compound (a) 7 was mixed with Tween 60 emulsifier (5 parts by weight) to yield a concentrate with an extender content of 95% by weight.

EXAMPLE IV

Preparation of wettable powder

A mixture of S-ethyl-N, N-di (n-propyl) -thiol carbamate (10 parts by weight), N, N, -dipropyl-N, N'-diallyldiaminomethane-20 extender (1 part by weight), ethyl polyglycol ether (1 part by weight) and kaolin (88 parts by weight) were ground in a ball mill. The total active ingredient content of the wettable powder obtained was 11% by weight, while the mass ratio of the herbicidally active ingredient to the extender was 10: 1.

This wettable powder can be spray applied after suspension in an appropriate amount of water.

EXAMPLE V!

Preparation of an emulsifiable concentrate 30 A mixture of S-ethyl-N, N-di (n-propyl) -thiolcarba size (70 parts by weight), N, N'-dipropyl-N, N'-diallyldiaminomethane as extender / 72 parts by weight; compound (c) _ / and N, N-diallyl-dichloroacetamide as antidote (6 parts by weight) was dissolved in the mixture of Tween 60 (5 parts by weight) and xylene (27 parts-35 parts). After dilution of the obtained emulsifiable concentrate with an appropriate amount of water, a stable 8-01 707 J «.

-14-.

emulsion suitable for spraying the surface to be treated.

EXAMPLE VI

Preparation of a granulate 5 N, N, N ', Ν'-Tetraallyldiaminomethane extender (10 parts by weight) was mixed with epichlorohydrin (2.5 parts by weight) and the resulting mixture was dissolved in acetone (70 parts by weight) ). Cetyl polyglycol ether (2.5 parts by weight) and polyethylene glycol (35 parts by weight) were added to this solution.

The resulting solution was sprayed on kaolin (950 parts by weight, particle size 0.5-0.9 mm), after which the acetone was evaporated under reduced pressure to yield a granulate containing 1% by weight of the extender, which granulate on the surface to be treated could be applied by scattering.

Using similar methods as described in the above examples, a suitable preparation. be prepared from any of the extenders listed in Table A, optionally using one or more thiol carbamate derivative (s) and / or antidote (s). A formulation may also be prepared with only extender in it or mixed with the appropriate additives.

The capacity of the extenders of the invention to delay the decomposition of thiol carbamate derivatives in the soil has been studied in laboratory tests.

The biological activity of the herbicide preparations containing an extender according to the invention, a thiolcarbamate derivative and possibly an antidote has been studied in greenhouse tests on the following plants: maize (Zea maize), barley 30 (Hordeum vulgare), wild oats (Avena fatua ), farm grass (Echinocloa crus-galli), millet (Setaria glauca), white mustard (Sinapis alba) and hairy amaranth (Amaranthus retro-flexus).

Based on these laboratory tests, it has been determined that the extenders according to the invention effectively delay the decomposition of thiol carbamate derivatives in the soil and are better than the known extenders.

It has been observed in the greenhouse tests that the herbicidal preparations with the extenders according to the invention contain 850 1 70 7

4 V.

- together with a thiol carbamate derivative (s) and possibly an antidote (s) have a stronger herbicidal effect than similar preparations without extender and exceed the herbicidal effect of the preparations containing the known extenders 5,

The activity of the extenders according to the invention is further illustrated by the following examples. The examples are non-limiting.

EXAMPLE VII

100-100 g of air-dried pretreated soil was transferred to a 250 ml Erlenmeyer flask. 1.39 ml of the commercially available Eptam 6E herbicide (EPTC) was mixed with 1 L of distilled water. 0.6 ml of the emulsion thus obtained was added to 5 ml of water, after which the emulsion was poured onto 100 g of soil. / The commercially available Eptam 6E contained 0.82 kg / l S-ethyl-N, N- di (n-propyl) thiol carbamate as active ingredient /. The above procedure was suitable for a treatment with 6 ppm of the thiol carbamate, calculated on the ground. Then 0.5-0.5 ml of 20 xylene was added to 1.05 g of samples of the emulsifiable concentrates prepared according to Example 3 containing the extenders according to the invention or diallylamine, the latter being used as a control, after which each of the thus ! Prepared solutions were suspended in 1 L of water. Of the 25 emulsions thus obtained, 0.4 ml was added to each of the soil samples, which were previously treated with the thiol carbamate derivative. This treatment was suitable for a 4 ppm dose of the extender calculated on the ground. Then water was added to the soil in an amount that the correct moisture of the soil was reached, but the soil was prevented from sticking together (30 ml of water was required for one flask). The soil in the flasks was thoroughly mixed using a glass rod, then the flasks were sealed with cotton wool to give the aerobic conditions, then thermostated (incubated) at 25 ° C in the dark for 4 days.

After the incubation, 100 ml of water and 50 ml of toluene were added to each of the soil samples, after which the suspension was 350 ml. was stirred mechanically at a high rotation speed for 10 min, after which the samples were discarded to separate the organic phase. The thiol carbamate content of the toluene phase was analyzed by gas 5 chromatography. The results of this determination were converted to the amount of the thiol carbamate active ingredient, calculated on the soil and expressed in ppm. The results of the persistence measured in soil are shown in Table B.

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On the basis of the results reported in Table B, it can be stated that the diaminomethane derivatives of the invention have inhibited the decomposition of EPTC to a greater degree than the most suitable secondary amines of the published Hungarian patent application no. 3383/82 did.

Based on similar experimental conditions, the results listed in Table B can be compared to the activity of the extenders, as shown either in Hungarian patent application no. 3383/82, or in Hungarian patent application no. 783/82. According to the latter patent application, the most active 4- [2'-N- (3 "-trifluoromethylphenyl) -carbamoyl-oxyphenyl] -1,2,3-thiadiazole was used as extender under identical test conditions after 4 days to be 2.37 ppm, which was inferior to the extenders of the invention.

EXAMPLE VIII

Under identical conditions to those described in Example VII, the dose of EPTC was unchanged, while extender used Ν, Ν, Ν ', N, tetraallyldiaminomethane in gradually decreasing (halved) doses. Di-allylamine, a known extender, was used as an extender. The results are included in Table C.

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It is clear from the results reported in Table C that the decomposition of EPTC in the soil was effectively prevented by the extender N, N, N ', N'-tetra-allyldiaminomethane even at such a dose that the case of diallylamine is inactive.

Practical tests have shown that the decomposition of thiol carbamates is much faster in soils that have been pretreated with thiol carbamate derivatives than in the untreated soils. The soil used for the experiments was pretreated in the following manner.

Pretreatment of a soil with S-ethyl-N, N-di (n-propyl) thiol carbamate

An unsterilized vegetable soil (with an organic material content of 2.2 to 2.5 g / 100 g and a pH-15 value of 6.5) was transferred in a thickness of 10 cm into plastic dishes of 30x30 cm. Three rows of corn (10 seeds each) and two rows of millet (Setaria glauca; 25 seeds each) were sown in the thickened and flattened soil at a depth of 1.5 cm. Immediately after sowing, 20 microliters of Eptam 6E herbicide emulsified in 50 ml of water was sprayed onto the soil surface of each of the dishes. This treatment was equivalent to transferring 5 l of preparation / ha in normal practice. The dishes were kept in a greenhouse at 20-25 ° C and sprayed for 21 days if necessary. Spraying was stopped on the 22nd day, after which the plants were removed along with their root system on the 28th day. The soil had been removed and sieved as air dry. The air-dry soil, free from plant residues, was used as "pretreated soil" for the further pilot studies.

EXAMPLE IX

Investigation of the herbicidal activity of the preparations according to the invention in a pretreated soil

The pretreated soil was transferred in a thickness of 8 cm in plastic dishes of 50x35 cm, thickened, after which the seeds of the following plants were sown in rows at a depth of 1.0-1.5 cm: corn, barley, wild oats , farm grass, millet, white mustard and hairy amaranth. Then 850 1 70 7 - 21 - 1 ml of toluene was added to 1.25 of a concentrate of 80 wt% S-ethyl-N, N-di (n-propyl) -thiol carbamate and 16 wt% of the extender ( a), while the emulsifiable concentrate thus prepared was mixed in 1 liter of water. A similar emulsion was prepared using diallylamine, a known extender in place of the extender (a).

A control without any extender was prepared by emulsifying 0.7 ml of commercially available Eptam 6E herbicide in 1 L of water.

Shortly after sowing, 100 or 50 ml of the above-mentioned emulsions were sprayed on the soil surface in each of the dishes, which corresponded to a treatment of 8.0 or 4.0 1 / ha Eptam 6E, calculated on the EPTC content of the preparations. The mass ratio of the thiol carbamate to the extender was 5: 1 in the formulations used.

The dishes were kept in a greenhouse at 20-25 ° C and sprayed if necessary. The condition of the plants was evaluated on the 20th day by measuring the growth length and by evaluating the appearance and condition of the plants compared to the untreated control. In Table D, the growth length is indicated as the percentage of the untreated control, while the condition of the plants is indicated by the numbers from 0 to 100, where 100 means a fully intact condition without any damage, while 0 means that the plants completely destroyed.

The results are reported in Table D.

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EXAMPLE X

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This test was carried out in the manner described in Example IX, except that the unsterilized soil was used without any pretreatment, while the soil was sprayed with emulsions containing EPTC in an amount corresponding to a treatment with a reduced amount of 3.0 1 / ha or 6.0 1 / ha Eptam 6E (i.e. 10 75 or 37.5 ml of the above emulsions). The results are reported in Table E.

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This run was performed in the manner described in Example X except that Vernolate 72 EC [s- (n-propyl) -N, N-di (n-propyl) -thiol carbamate werd was used instead of Eptam 6E. The results are reported in Table F.

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Claims (10)

1. A preparation for extending the action of the bicides, with the active ingredient a thiol carbamate derivative and optionally antidote, characterized in that a diaminomethane derivative of the general formula 3 of the formula sheet, wherein the R substituents are independently of each other. -g alkyl groups or C 2-4 alkenyl groups, optionally substituted by a C 1-4 alkyl group, are present in the composition as the active ingredient. 2. Herbicide preparation with extended action, characterized in that the herbicidal active ingredient preparation contains a thiol carbamate derivative and a diaminomethane derivative of the general formula 3 of the formula sheet for achieving the prolonged action. 3. Selective herbicide preparation with an extended action, characterized in that the preparation as herbicidally active ingredient contains a thiol carbamate derivative, then an antidote for promoting selectivity and a diaminomethane derivative of the general formula 3 of the formula sheet for obtaining the extended operation. Preparation according to claim 2 or 3, characterized in that one or more thiol carbamate derivative (s) of formula 1 of the formula sheet, wherein R 1, R 2 and R 1 independently represent a C 1-4 alkyl group 25 ; or R.j or R2 represents a C4-8 cycloalkyl group; or R.j and R2 together represent a saturated ring having 5-7 ring atoms are present in the composition. - 5. Preparation according to claim 3 or 4, with the! characteristic, that as an antidote one or more dichloroacet-! ! amide derivative (s) of the general formula (2) of the formula sheet are present in the composition, in which formulas R4 and Rg independently of one another have a C2-4 alkenyl group, a (^ -4 alkoxy) - (C1-4 alkoxy) - (C1-4 alkyl) group, or suggest a (C2-4 alkenyl) -arainocarbonyl- (C1-4 alkyl) group? or R4 and Rjj together represent a saturated ring with 4-7 ring atoms, optionally interrupted by an acid atom of 8501707 * - 28 and optionally substituted with up to three methyl groups or C 1-6 cycloalkyl groups, or 2-methyl-2-dichloromethyl dioxolane or 1,8-naphthalenedicarboxylic anhydride. A composition according to any one of claims 1 to 5, which composition contains the following ingredients: Ν, Ν, Ν ', Ν' - tetraallyldiaminomethane, N, N'-diethyl-Ν, Ν1-diallyldiamino-methane, N / N "-dipropyl-N ^" - diallyldiaminomethane, N, N'-diisopropyl-N, N1-diallyldiaminomethane, N, N1-diisobutyl-Ν, Ν1-diallyl-10 diaminomethane, or N, N'-diallyl-Ν, Ν'-di (2-methylallyl) -diamino-methane for prolonging action. Preparation as in the preceding claims 2-6, characterized in that the preparation as thiolcarbate derivative contains the following compounds: S-ethyl-N, N-di-15 (n-propyl) -thiol carbamate, S- ( n-propyl) -N, N-di (n-propyl) -thiol carbamate, S-ethyl-N, N-diisobutylthiol carbamate, S-ethyl-N, N-hexamethylene thiol carbamate, S-ethyl-N-cyclohexyl-N ethyl thiol carbamate and / or S-propyl N-butyl N-ethylthiol carbamate. A preparation according to any one of claims 3-7, 20, characterized in that this preparation contains as antidote the following compounds: N, N-diallyldichloroacetamide, N-allyl-N- (ethoxyethoxymethyl) -dichloroacetamide, 2,2,5 -tri-methyl-N-dichloroacetyloxyzolidine, N, N-hexamethylenedichloroacetamide, 2-cyclohexyl-3-dichloroacetyloxazolidine, N-allyl-25 -N-dichloroacetylglycine allylamide, 2-methyl-2-dichloromethyl-dioxanolide or dioxolane . 9. Method for extending the action of herbicidal preparations containing a thiol carbamate derivative and optionally an antidote, characterized in that the preparation according to claim 1 in an amount necessary for the prolonged action simultaneously with or after application of the herbicide preparation is applied. 10. A method according to claim 9, characterized in that the treatment is carried out with a composition according to claim 2 or 3. 850 1 70 7